Mixed sulfite esters of aryl glycol ethers and alkynols



United States Patent 3,179,682 MIXED SUIFH'E ESTERS 0F ARYL GLYCOLETI-ERS ANT ALKYNOLS Rupert A. Covey, Wolcott, Allen E. Smith, Oxford,and Winchester L. Hubbard, Woodbridge, Comm, assignors to United StatesRubber Company, New York, N.Y., a corporation of New Jersey No Drawing.Filed Aug. 20, 1962, Ser. No. 218,090

6 Claims. (Cl. 260-456) This application is a continuation-in-part ofour application Serial No. 131,741, filed August 16, 1961, and nowabandoned.

This invention relates to new chemicals, namely new organic esters ofsulfurous acid, more particularly to mixed sulfite esters of alkynylalcohols and glycol ethers.

The new compounds of the present invention are useful as insecticides,particularly for the control of mites. They may also be used asplasticizers.

The chemicals of the present invention may be represented by the generalformula in which R is an aromatic radical, eg. phenyl, or naphthyl, or aphenyl or a naphthyl (aryl) radical having one or. more substituents inthe aryl nucleus selected from the group consisting of alkyl having upto 9 carbon atoms, cycloalkyl, haloalkyl, alkoxy, nitro and halo; R isan acyclic alkynyl radical; n is 2 to 10, and m is 1 to 10. Where m isgreater than 1, the repeating oxyalkyl groups may be the same ordifferent. Examples of R are phenyl, l-naphthyl, Z-naphthyl, p-tolyl,o-tolyl, isopropylphenyl, tert.-butylphenyl, tert.-amyl phenyl,nonylphenyl, cyclohexylphenyl, chloromethylphenyl, methoxyphenyl,nitrophenyl, and haloaryl having up to halo radicals, e.g. bromophenyl,2-chlorophenyl, 2,4-dichlorophenyl, trichlorophenyl, pentachlorophenyl.Examples of R are acyclic alkynyl radicals having 3 to 10 carbon atoms,i.e. C l-l radicals where n is 3 to 10, e.g. propargyl, 1- (3-butynyl 2-(3 butynyl) 2-(2-metl1yl-3-butynyl) .1-(2-heptynyl), 1-(3-nonynyl).Examples of the group are ethyleneoxy, trimethyleneoxy,tetramethyleneoxy, propyleneoxy, 1,2-dimethylethyleneoxy.

The preparation of the chemicals of the invention may be carried out byreacting the selected alkynyl alcohol with the separately preparedchlorosulfinate of the selected glycol ether, which may be made byreacting the selected glycol ether with thionyl chloride. The glycolether which is a glycolmonoether may be made by reacting the selectedphenol, with one to ten moles of the selected alkylene oxide per mole ofthe phenol. Such preparation is illustrated by the following reactionswith the same symbols R, R and m as in the above general formula and forconvenience using ethylene oxide (11:2) as the alkylene oxide:

3,179,682 Patented Apr. 20, 1965 ice Reaction (1) above is a well knownand smooth reaction. With one mole of alkylene oxide per mole of phenol,the result will be substantially a single compound containing onealkylene oxide unit. With two or more moles of alkylene oxide per moleof phenol, a mixture of products having varying numbers of alkyleneoxide units is produced. it a compound with a specific number ofalkylene oxide units is desired, the mixture may be fractionated. In thepresent invention for insecticidal uses, it is satisfactory to havemixtures of compounds containing dilferent numbers of alkylene oxideunits from 1 to 10. The following reaction of p-tert.-butyl phenol withpropylene oxide is illustrative of the well known preparation of thestarting glycol ethers according to reaction (1) above:

p-Tert.-butyl phenol (300 g., 2.0 moles) and 4 g. sodium hydroxide werecombined and the mixture heated to C. Propylene oxide (279 ml., 232 g.,4.0 moles) was added during two hours maintaining the reactiontemperature at 150-160" C. The mixture was cooled, the catalyst wasneutralized with dilute hydrochloric acid, and the product taken up inbenzene. The benzene was removed and the product heated to 90 C. (0.5mm.) to remove the last traces of volatile materials. The crude reactionmixture weighed 509 g. (95.7%). It was a mixture of compounds having thestructure where m=1, 2, 3, 4, 5, etc. The mixture was distilled and thefollowing fractions collected:

. Percent m =1, B.P. 107-128 C. (1 mm.) s 32 m ==2, B.P. 128-153 C. (1mm.) 47 m =3, B.P. l=63-184 C. (1 mm.) 14 Residue 7 Center cuts of thesefractions yielded the pure compounds as follows:

m=1, B.P. 116-120" C. (1 mm.)

m=2, B.P. 146153 C. (1 mm.)

m1=3, B.P. 177 C. (1 mm.)

The preparation of the chlorosulfinates of the glycol ethers accordingto reaction (2) is carried out. at a temperature of between 5 C. and 30(1., preferably near 0 C., and the yield of chlorosulfinate is nearlyquantitative. An inert solvent such as benzene, xylene or solventnaphtha may be used. This is illustrated in Example I below. 1

The preparation of the sulfite esters is carried out in the presence ofan HCl acceptor, such as pyridine, dimethyl aniline or trimethylamine,and in a solvent such as benzene, xylene or solvent naphtha. Thereaction temperature is generally between 10" C. and 50 C., preferablynear 0 C. This is illustrated in Example I below.

Examples of the sulfite diesters of the present inven tion are:

Propargyl phenoxyethyl sulfite Propargyl o-toloxyethyl sulfite Propargylm-(n-propyDphenoXyethyl sulfite Propargyl p-tert.-amylphenoxyethylsulfite Propargyl p-chlorophenoxyethyl sulfite Propargyll-naphthoxyethyl sulfite amaeaa Example 1 illustrates the preparation ofthe compounds of the present invention.

EXAMPLE I Preparation of propargyl p-tert.-butylphenoxyisopropyl sulfitep-Tert.-butylphenoxyisopropyl chlorosulfinate was prepared asillustrated in reaction (2) above as follows:ptert.-butylphenxyisopropyl alcohol or propylene glycol mono-p-tert.butyl phenyl ether (104 g., 0.5 mole) prepared according to reaction (1)as described above was dissolved in 150 ml. benzene and the solution wascooled to 0 C.- C. Thionyl chloride (45.4 ml., 74.4 g., 0.625 mole) wasadded dropwise during one hour, maintaining the reaction temperaturebelow 5 C. The mixture was allowed to warm to room temperature and standfor hours. The benzene wasevaporated under reduced pressure at roomtemperature and the residue was warmed to 35 C. (0.8mm.) to remove thelast traces of solvent. Yield, 141.3 g. (97.3%) of a pale yellow oilwhich was nearly odorless and relatively stable when stored in arefrigerator.

The propargyl p-tert.-butylphenoxyisopropyl sulfite was prepared asillustrated in reaction (3) above as follows: propargyl alcohol (3.2ml., 3.1 g., 0.055 mole), 4.1 ml. (4.0 g., 0.05 mole) pyridine and 30ml. xylene were combined and the solution cooled to 0 C.5 C. A solutionof 14.5 g. (0.05 mole) p-tert.-butylphenoxyisopropylchlorosulfinate in10 ml. xylene was added during 10 min. keeping the reaction temperaturebelow 5 C.

The mixture was stirred for /2 hour and was washed twice with m1.portions of water. The mixture was then stirred for one hour with 50 ml.2 N NaOH. The xylene solution was washed several times with saturatedsalt solution until the washings were neutral to pH paper. The xylenewas removed under reduced pressure and the residue heated to a pottemperature of 140 C. (0.2 mm.) to remove volatile materials. Theproduct was filtered through Dicalite (a diatomaceous earth filter-aid)giving 13.9 g. (89.7% yield) of an amber-colored oil.Analysis.Calculated for C H O S: S, 10.33%. Found: S,

Sulfur analyses of other chemicals of the present in vention were:

Propargyl p-tert.-butylphenoxyisopropoxyisopropyl sulfite. Calculated S.8.70%. Found: 8.18%.

Propargyl p-tert.-'butyldiisopropoxyisopropyl sulfite. Calculated'S,7.52%. Found: 6.51%.

Propargylp-tert.-amylphenoxyethyl sulfite. Calculated A Propargyl1-paratertiarybutylphenoXy-2-amyl sulfite. Calculated S, 9.48%. Found:8.58%. V

Propargyl o-toloxyisopropoxyisopropyl sulfite. Calculated S, 9.82%.Found: 9.11%.

Propargyl p-tolyloxyisopropoxyisopropyl sulfite. Calculated S, 9.82%.Found: 8.74%.

Propargyl p-isopropylphenoxyethoxyethyl sulfite. Calculated S, 9.82%.Found: 8.99%.

Propargyl p-isopropylphenoxyisopropoxyisopropyl sulfite. Calculated S,9.05%. Found: 8.60%.

Propargyl 1-( 1-paraisopropylphenoxy-Z-butoxy)-2butyl sulfite.Calculated S, 8.42%. Found: 7.60%..

Propargyl 2-methyl-4-tert.-butylphenoxyisopropoxyisopropyl sulfite.Calculated S, 8.38%., Found; 7.74%.;

l-(3-butyny1) p-tert.-arnylphenoxyethyl sulfite. Calculated S, 9.88%.Found: 9.89%.

2-(3-hutynyl) ptert.-arnylphenoxyethylsulfite. Galen-- lated S, 9.88%.Found: 9.38%.

1-(3-hexynyl) p-tert.-amylphenoxyethyl'sulfite. Calcu lated S, 9.10%.Found: 8.73%.

2-(3-butynyl) o-tert.-butylphenoxyisopropoxyisopropyl sulfite.Calculated S, 8.38%. Found: 7.57%.

1-(2-butynyl) p tert.-amylpl1enoxyethyl sulfite. Calculated S, 9.88%.Found: 8.93%.

2-(2-methyl-3abutyny1) p tert. butylphenoxyisopropyl sulfite. CalculatedS, 9.48%. Found: 8.64%.

EXAMPLE II This example illustrates the insecticidal activity of thechemicals of the present invention in tests against the larvae of Aedesaegypti (L.) mosquitoes. Fourth instar larvae were used. Theselarvaenormallyreach this stage in' 5 days at F. after hatching.

To 10 mgs. of each chemical to be tested was added 1 ml. of acetone andml. of water to give a concentration of 100 parts per million (p.p.m.),and a portion was also diluted to 10 p.p.m.

Twenty-five ml. aliquots, replicated once, of each chemical to be testedat concentrations of 100 ppm. and 10 ppm. and of checks Without thechemical and of plain water checks were placed in test tubes and from 5to 25 larvae were added. The tubes were heldat 70 F. in darkness for 72hours. At the end of this period the live and dead larvae were countedand the percent mortality calculated. All the larvae were alive in thechecks (0% mortality). The percent mortality of the larvae treated withthe chemicals of the present invention is shown in the following table:

Percent tlvlortality a Chemical 100p.p.m. 10 p.p.m.

Propargyl p-tert.-butylphenoxy-isopropyl sulfite. 100. 100 Propargylp-tert.-butylphenoxy-lsopropoxyisopropyl sulfite 100 60 Propargylp-tert.-butylphenoxy-diisopropoxylsopropyl sulfite 100 41 EXAMPLE, III

This example illustrates the effectiveness of the chemicals of thepresent invention for controlling mites.

Pinto beans in the two-leaf stage and grown ,in 4"' The plants weresprayed with the dispersions of the chemicals at the variousconcentrations and the check plants were sprayed with aqueous solutionscontaining surfaceactive agent and acetone without the chemicals. Thesprayings thoroughly wet the upper surface of the leaves. The plantswere returned to the greenhouse. The following day (-24 hours later),rings of an adhesive preparation non-toxic to the organisms under test,such as is used on fly papers and for ringing trees, were placed aroundthe borders of the upper surfaces of the leaves to restrict themites tothe upper leaf surface. Mites were transferred to the thus treatedleaves by placing bean leaflets heavily infested with two-spotted adultmites, T etranychus telarius L. within the boarder of the adhesivepreparation on the leaves of the plants under test. A count of thenumber of mites transferred was made the same day. The counts rangedfrom to 300 mites on the six leaves. The plants were kept in thegreenhouse for another four days. A final count of the number of livingmites remaining on the leaves was then made. The percent control isfound by using the formula:

Percent con U01: l00 1 F1nal count living flutes) Original countPercenttcoutrol a Chemical 1,000 200 p.p.m. p.p.m.

Propargyl p-tert.butylphenoxyisopropyl sulfite.-. 99 lropargylp-tert.-butylphenoxyisopropoxyisopropyl sulfite. 99 Propargylp-tert.-butylphenoxydiisopropoxylsopropyl sulfite 99 90 Propargylp.terLamylphenoxyethyl sulfite 100 100 Propargylo-tert.-butylphenoxyisopropoxyisopropyl sulfite 100 100 1-(3-Butynyl)p-tert.-amylphenoxyethyl su1fite 100 96 2-(3-Butynyl)p-tert.-amylphenoxyethyl sulfite 100 99 2-(2-Methy1-3-butynyl)p-tert.-amylphenoxyethyl sulfite 100 84 1-(3-Hexynyl)p-tert.-amylphenoxyethyl sulfite.- 76 30 2-(3-Butyny1)o-tert.-butylphenoxyisopropoxyisopropyl sulfite 100 73 1-(2-Butynyl)p-tert.-amylphenoxyethy1sulfite 100 99 Propargyl p-toloxyisopropylsulfite 78 Propargyl l-paraisopropylphenoxy-Q-butyl sulfite 98 Propargylp-tert.-aruylphenoxyisopropyl sulfite 100 100 Prorligrgyl1-paratertiarybutylphenoxy-2-butyl 97 su Propgrgyl lparatertiaryamylphenoxy-Z-butyl 100 s PropargylB-paratertiarybutylphenoxy-Z-butyls fite 97 77 Propargyl1-paratertiarybutylpheuoxy-Z-amyl sulfite. 100 Propargylo-toloxyisopropoxyisopropyl sulfite- 80 Propargylp-toloxyisopropoxyisopropyl sulfite 77 Propargylp-isopropylphenoxyethoxyethyl sultite-. 64 Propargylp-isopropylphenoxyisopropoxyisopropyl sulfite. 100 99 Propargyl1-(l-paraisopropylphenoxy-2-butoxy)- 2butyl sulfite. c 96 Propargyl2-methyl-4-p-tert.-butylphenoxylsopropoxyisopropyl sulfite 99 Propargylp-tert.-l)utylphenoxyethoxyisopropyl sullite 99 86 EXAMPLE IV Thisexample also illustrates the effectiveness of the chemicals of thepresent invention for controlling mites.

Pinto beans in the two-leaf stage and grown in 4 baskets undergreenhouse conditions at 70 F.75 F. were used. Two plants for a total offour leaves were in each basket for each test. These tests on thechemicals were replicated once.

The untreated leaves were ringed with adhesive and 40-50 mites weretransferred to each leaf similarly to Example III.

The plants were then sprayed to thoroughly wet the upper surface of theleaves with aqueous solutions of the Percent; Control a Chemical 50p.p.m. 20 p.p.m.

Propargyl p-tert.-butylphenoxy-isopropyl sulfite.-- 84 Propargylp-tertbutylphenoxy-isopropoxyisopro- 9 87 The chemicals of the presentinvention may be applied in various manners for the control of insects.They may be applied to loci to be protected against insects as dustswhen admixed with or adsorbed on powdered solid carriers, such as thevarious mineral silicates, e.g. mica, talc, pyrophillite and clays, oras liquids or sprays when in a liquid carrier, as in solution in asuitable solvent, such as acetone, benzene or kerosene, or dispersed ina suitable non-solvent medium, for example, water. In protecting plants(the term including plant parts) which are subject to attack by insects,the chemicals of the present invention are preferably applied as aqueousemulsions containing a surface-active dispersing agent, which may be ananionic, non-ionic or cationic surface-active agent. Such surface-activeagents are well known and reference is made to US. Patent No. 2,547,724,colums 3 and 4, for detailed examples of the same. The chemicals of theinvention may be mixed with such surface-active dispersing agents, withor without an organic solvent as insecticidal concentrates forsubsequent addition of water to make aqueous suspensions of thechemicals of the desired concentration. The chemicals of the inventionmay be admixed with powdered solid carriers, such as mineral silicatestogether with a surface-active dispersing agent so that a wettablepowder may be obtained, which may be applied directly to loci to beprotected against insects, or which may be shaken up with water to forma suspension of the chemical (and powdered solid carrier) in water forapplication in that form. The chemicals of the present invention may beapplied to loci to be protected against insects by the aerosol method.Solutions for the aerosol treatment may be prepared by dissolving thechemical directly in the aerosol carrier which is liquid under pressurebut which is a gas at ordinary temperature (e.g. 20 C.) and atmosphericpressure, or the aerosol solution may be prepared by first dissolvingthe chemical in a less volatile solvent and then admixing such solutionwith the highly volatile liquid aerosol carrier.

The chemicals may be used admixed with carriers that.

are active of themselves, for example, other insecticides, fungicides orbactericides.

Having thus described our invention, what we claim and desire to protectby Letters Patent is:

1. A chemical represented by the general formula in which n is 2 to 10,m is 1 to 10, R is selected from the group consisting of phenyl,naphthyl, phenyl and naphthyl having substituents consisting of up to 5halo radicals selected from the class consisting of bromo and chloro,and mono-substituted phenyl and naphthyl having the substituent selectedfrom the group consisting of alkyl having up to 9 carbon atoms,cyclohexyl, chloromethyl and rncthoxy, and R is acyclic alkynyl of theformula C H Where n is 3 to 10.

2. Bropargylp tert.-butylphenoxyisopropoxyisopropyl sulfite.

3. Propai gyl -p -tert.-butylphen0xydiisopropoxyisopro- References Citedby the Examiner UNITED STATES PATENTS Hester 167-30 Harris et a1. 260456Van Strien 167-30 Lawlor 260-456 Boyack et a1. 71--2.6 Fischer 71-2.6Schafer et a1 71--2.3 Winneman et a1. 71-2.3

CHARLES :B. PARKER, Primary Examiner.

1. A CHEMICAL REPRESENTED BY THE GENERAL FORMULA